Tricyclic polysulfur compounds and process for their preparation

ABSTRACT

Novel polysulfur tricyclic compounds wherein two substituted aromatic rings are attached to each other through two tetrasulfide links.

United States Patent Zaven S. Ariyan Woodbury, Conn.;

Robert L. Martin, Endicott, N.Y. 804,998

Mar. 6, 1969 Nov. 16, 1971 Uniroyal, Inc.

New York, N.Y.

lnventors Appl. No. Filed Patented Assignee TRlCYCLlC POLYSULFURCOMPOUNDS AND PROCESS FOR THEIR PREPARATION 13 Claims, No Drawings [51int. C1.....I;.TI'.1.'...'.' c070, 77 00 C08c 11/60 [50 Field of Search260/327 B, 1: 327 R {56] References Cited j OTHER REFERENCES Ariyan, etal., J.C.S. 4,709- 4712 (1962).

Primary Examiner-l-lenry R. .liles 1 Assistant Examiner-Cecilia M.Shurko Att0rneyWillard R. Sprowls TRICYCLIC POLYSULFUR COMPOUNDS ANDPROCESS FOR IR P l?? Tl FIELD OF INVENTION Polysulfur tricyclic systemswherein two substituted aromatic rings are attached to each otherthrough two tetrasulfide links forming a central ring structurecontaining eight sulfur atoms.

PRIOR ART Although applicants are not aware of any prior art that isrelevant to the invention, a brief discussion of the background inchemistry underlying the present invention may facilitate its,

appreciation. V

represented by the following equations:

There is no reported example in the chemical literature of two aromaticrings attached to each other by two sets of chains of sulfur atoms suchas the replacement of the methylenes in [2.2] paracyclophane (II) bysulfur atoms. About sixty years ago, [W. Autenrieth Ber. 41, 4249(I908); 42, 4346 (I909)] described a l6-membered and an l8-membered ringsystem (III and IV) derived respectively from metaxylylene dithiol andpara-xylylene dithiol.

(III) SUMMARY OF INVENTION The invention relates to novel tricyclicsystems in which two aromatic rings are attached to each other by twotetrasulfide links. The novel tricyclic systems may be represented bythe formula (I) l O l wherein X is alkoxy (OR), alkylthio (SR) orhalogen, R being represented by straight or branched alkyl, hereinafterreferred to as "cyclic-bis-tetrasulfides" or CBT.

The invention is also concerned with a novel process for preparing thenovel cyclic-bis-tetrasulfides.

Considered from an other aspect, the invention relates to novelcompounds obtained by the splitting of CBT.

As will be noted from formula I of the novel cyclic-bistetrasulfides,the positions of substitution by the sulfur atoms onto the aromaticrings may vary and are in fact determined by the respective substituentson the ring.

The aromatic rings themselves are disubstituted with at least one alkoxygroup, a thioalkyl group or a halogen. The ring substituents arepreferably situated in para-positions respective to the ring. In formulaI, X represents either an alkoxy group O-R; an alkylthio group S-R or ahalogen. Chlorine is a suitable halogen for the inventive purposes. Rmay be any 0 alkyl group, either straight or branched. Preferred alkylsare the lower alkyls of from one to five carbon atoms.

The size of the central sulfur ring is determined by the position ofsubstitution of the sulfur atoms which may occur at 223-; 2:5--;or, 2:6-depending on the nature of the ring substituents and particularly of X.

The cyclic-bis-tetrasulfides are high melting, yellow to deep orangecrystalline products whichmay be readily prepared by the reaction of apara-substituted alkoxybenzene with sulfur monochloride (Cl-S-S-Cl) inthe presence of a catalyst. The reaction is advantageously carried outat elevated temperatures within the temperature range of about 40-70 C.A convenient catalyst for the reaction is a Lewis acid type catalyst,

such as anhydrous aluminum chloride, boron trifluoride, tin or antimonychlorides and, preferably, a montmorillonite catalyst of the K-series"which is readily available from Chemical Products Division of ChemetronCorporation and designated hereafter Girdler Catalyst KSF/O." It hasbeen found that the presence of a catalyst is of utmost importance forthe preparation of the cycIic-bis-tetrasulfides. A diluent should alsobe present. Suitable diluents are carbon disulfide, chloroform, carbontetrachloride, methylene dichloride, ethylene dichloride or, in general,halogenated aliphatic hydrocarbon solvents. Reaction at the boilingtemperature of the solvent or diluent is preferred. Most of theindicated solvents boil within the indicated preferred 4070 C. range.

In the preparation of the cyclic-bis-tetrasulfides, the parasubstitutedalkoxybenzene is vigorously stirred in the solvent with 5 percent byweight of the catalyst, to which is added sulfur monochloride(Cl-S-S-cl. in the same solvent. After complete addition of the sulfurreagent and if no reaction is apparent, heat, for example, in the formof steam is applied.

Invariably hydrogen chloride gas begins evolving after all the sulfurmonochloride has been added and the reaction mixture assumes a deepgreen color, due to the formation of a complex intermediate. Thereaction mixture is thus stirred and heated until all the hydrogenchloride gas has evolved. The deep green color has also disappeared atthat time. The reaction time may vary from 2 to 5 hours. The reactionmixture is then filtered while hot to cause separation from the catalystand an orange solution results. Some of the solvent may have to beevaporated off to allow crystallization of the product. As will be seenfrom the examples given hereinbelow, in some cases work-up methods arerequired whereas in others the products are relatively insoluble andprecipitate from the solution. For

example, on standing of a reaction product solution obtained fromp-diethoxybenzene, large orange crystals appear, while: an extremelyinsoluble orange product is obtained from pdimethoxybenzene. Both theseproducts are cyclic-bistetrasulfides. In the case of insoluble productssoxhlet extraction method may have to be used to remove the product fromthe catalyst, since filtration of the hot reaction product solution doesnot yield the desired separation. In respect to other derivatives,column chromatography on alumina is invariably of value, since anyelemental sulfur is then removed on the alumina.

The orange crystals consist of the novel CBT compounds. Their structurehas been supported by a variety of physical methods. Such methods asX-ray, Nuclear Magnetic Resonance (N.M.R.), Ultraviolet (U.V.), Infrared(I.R.), molecular weight and elemental analysis have been used toelucidate and conclude on the crystalline .nature of these compounds.

A general scheme for the reaction steps may be represented by thefollowing:

Although applicants do not want to be limited by any theories advancedby them it is believed that the first step in the r q sa is-9bqqithiqzqqivfiixs formation (C &1; S-S-AQCI) where Zrepresents adivalent radical such as a para-substituted alkoxybenzene. Suchintermediates from sulfur monochloride reactions are known and have beenreported in J. Chem. Soc. 1725 (I962).

t t 8 ep Lewis acid catalyst Step two involves the formation of anintermediate with loss of chlorine. Evidence for such reactions isavailable in the' atst -fl- Step three is a step similar to step two,whereby another mole of chlorine is lost intramolecularly (within thesame molecule) by a mechanism which favors such a cyclization to yieldthe inventive cyclic-bis-tetrasulfide of formula l. H v

Step (3) S S S S tetramethylthiuram disulfide, which is also known underthe 'trademark TUEX, indicated that the former compound is superior toTUEX in the vulcanizing of SBR.

The inventive CBT compounds may be degraded or split into useful newcompounds. Depending on the splitting process to which the CBT compoundsare subjected, the following three groups of compounds may thus beobtained:

wherein X and R have the above meaning.

Compounds of group A are para-substituted alkoxybenzenes with twomercapto groups and thus constitute aromatic dithiols which are obtainedby the hydrogenation of CBT under controlled conditions. By contrast,chlorination under anhydrous conditions in a nonpolar solvent, such ascarbon tetrachloride, degrades CBT to reactive compounds of group B,such as disulfenyl chlorides. Compounds of group B are difficult toisolate and are thus used in situ. Chlorination of CBT in the presenceof trace amounts of water in turn yields disulfonyl chlorides of groupC.

Compounds A, B and C are bifunctional. They constitute new compositionsof matter, have utility per se, and may be successfully used in avariety of syntheses for the preparation of other useful compounds.

The primary utility of the compounds A, B and C is herbicidal andfungicidal.

The scheme for obtaining the compounds A, B and C may be demonstrated bythe following:

wherein Z represents the para-substituted alkoxybenzene rings of formulaI.

In order to appreciate this aspect of the invention, it should beconsidered that there is no direct convenient way of preparingdimercapto-(p-substituted alkoxybenzenes) or (alkoxy,alkylthio)-benzenes. This invention, for the first time, proposes suchderivatives Z-(Sl-I), designated (A); their chlorinatio n pr odu (:ts Z-(SCI) designated (B), which are TABLE I.R AND X IN FORMULA 15"Oaleulated Found Melting General R X point formula C H S Cl C H S 01 CH3OCH3 210-215 Curl-1 90483 36. 31 3. 05 48. 51 48. 36 C OC2H5 C H O B 41.07 4. 13 43. B6 44. 24 CH; O CgHr 15860 (31111 200438 38. 82 3. 62 46.07 46. 11 CH Cl -8 (314111 0201 8 31. 27 1. 88 47. 68 47. 53 13. 06Phony OCHz Pll 172-5 C4oH32O S5 57. 66 3. 87 30. 79 c 3 63 normally usedin situ, and their oxidation products Z(SO,Cl

I 70 designated (C).

It is well known that in sulfur monochloride reactions, polymers oftenoccur due to lengthening of the chains by sulfur atoms. In the formationof the inventive cyclic-bis-tetrasultides (CBT) which are formed throughintermediates 75 (CLSS-R-S-SCI), straight chain polymerization compoundsare also obtained. As a matter of fact and as has been statedhereinabove, after separation of the crystalline cyclic compounds, anorange-colored oil is also obtained. This oil is a polysulfur linearpolymer represented by the formula V, wherein n=2 or 4 and Z ispara-substituted alkoxybenzene:

Therefore polymers of type V are formed, but their degradation wouldalso yield the compounds of groups A, B and C.

it has thus been found that the oily linear polymer products designatedby V are also reduced to the same aromatic dithiols as theircorresponding cyclic crystalline products (CBT). The reaction productsobtained in the preparation of CBT may thus be subjected directly toreduction without further separation of the crystalline products and theorange colored oil.

similar to R; X may also be a halogen. The group A compounds may befurther reacted to prepare a variety of bis-sulfides, disulfides andpolysulfides as shown in table 111.

Reactions of compounds of group A with:

1. aliphatic or aromatic compounds containing a reactive halogen willyield bis-monosulfides.

10 where Z is the p-suhstituted alkoxybenzene, X a halogen, and

R" either an aliphatic branched or unbranched hydrocarbon or substitutedor unsubstituted aromatic ring. Methyl, ethyl, butyl, tert-butyl,phenyl, nitrophenyl, 2-chloro-4-nitrophenyl,

polychlorophenyl compounds may thus be prepared. Table 111 merely listsa few possibilities in the series where x=l.

2. with aliphatic or aromatic sulfenyl halides R"SCl, bisdisulfides areobtained. 2R"'SX+HS-t ,Z)-SH R"-S-S(Z) S-S-R"'+2HX Reduction Products ofCBT Compounds The controlled hydrogenation of CBT results in reductionto aromatic dithiols of group A. Such a process may advantageously becarried out with a platinum sulfide catalyst supported on carbon. Thehydrogenation is performed in a solvent, such as benzene or toluene, foran average period of 4 hours at a temperature of about 200 C. and at apressure range of 900 l ,300 p.s.i.g. See table 11.

TABLE II Calculated Found Melting Posi- General R X point tion form C HS 01 C H S C1 C211 OCQHE 117 2-.5 CroHuO2S2 52.17 6.09 6.29 27.5 CH3 Cl43.5-44 2:6- 0111108201 40.66 3.41 3.82 31.95 18.09 CH3 ()CzHa 2:5CrHrzOzSz 49.97 5.58 5.49 29.08 C411 00.1110 77-78 2:5 CHI-1220282 58.707.74 7.71 22.44 C113 ()(l lla 122 2:5 CaHrnOaSz 47.40 4.98 5.13 31.50

nitrophenyl-, dinitro-phenyl-, methyl-nitrophenyl-, naphthyb,substituted naphthyl-. anthraquinonyland derivatives and combinations ofany substituents for which the corresponding sulfenyl halide may readilybe available. Table III lists a few examples where x=2 A few examplesare here given of the feasibility of this reaction in obtaining a seriesof aromatic dithiols. The nature of R has previously been defined as abranched or unbranched 5O aliphatic chain of carbon atoms, preferably C-C and X may be an alkoxy (-OR') and alkylthio (-SR') where R may be R Os RI R's.

TABLE III Calculated Analyzed Melting Posi- X R R x point tion Generalformula C H H Cl Ethoxy EthyL Methyl 1 109-11 2:5 CnHraOzSz 55.78 7.086.92 Same..." Same. Ethyl 1 7848.5 2:5- C14H2102$2 58. 69 7. 74 7. 84 Do.do...n-Propyl 1 7848.5 2:5- CitHztOzSz 61.11 8.33 8.60 D0. ..dO...iso-Propyl 1 71-72 225- 01011150232 61.11 8.33 8.33 Do ..do n-Butyl 178-79 2:5- CraHanOzSz 63.20 8.84 0.04 D0 "d0... sec-Butyl 1 17-18 215-CmHaoOrSfl 63.20 8.84 8.55 l)o..... .do...n-Amyl 1 56-57 2:5-02011340282 65.01 9.25 9.62 Do do.. n-lloxyl 1 37-30 2:5 0221135028266.28 0.55 0.31 l)o .do v tlyt-lohoxyl 1 78-70 2:15 02211340 8: 66.618.63 8.80 Do do -Nltrophonyl 1 205 -11 216 0221120058 17? Do .dolrlt'hlorolnuthyl 2 -20 2:5 (l 11120234015 Do .do llonzoyl 1 180-1 2:5-Cull-110482 l)o do O'Nlll'OPlllllYl 2 2:5-- CzzllznOaSrNz l)o .mdo...Pontneiloroplieuyl 2 205 2:5- 0111112028401; Do .do. 2:4 dlnltroplienyl2 108-0 2:5- C- Hrg0mS4N4 [)0 do.. 2-ultrn-4-ohl0t'opl1enyl 2 2078 2:5-C22HiaOB 4C12N2 Do. .do ll-tmtliryl 3 165-6 2:5 01 1128028 or. R 2.7.. A

- S Or-R' l O R TABLE IV Calculated t Analyzed Melting General B R pointformula C H S Cl N C H S Cl N Methyl Chlorine 214- CsHsOeSzCh 28. 672.41 19.13 21.15 28. 70 2. 47 10.40 21.09 Ethyl Chlorine 190-1C10H12OaS2C1z 32.99 3.32 17. 62 19. 48 33.40 3.27 18. 48 19. 50 MethylAmino 300 CBHI205S2N2 21.6& .46 0.18 8. 88 Ethyl n-Butylarnino 167-8 C5Ha2OsS2N2 64 Ethyl Cyclohexylamino 255-256 C22HaoOeS2N2 Nora: Certainbis-sulfonamides have been listed in Table IV. 3. with chlorodithioderivatives (RSSC1) or derivatives (R S,,C) where n=2 or greater.

Table III lists an example of this reaction.

The above thus relates to the compounds of Group A as useful productsfor a series of synthesis.

Products of type R'-S-S(Z)SS-R"' may also be obtained by the anhydrouschlorination of CBT in carbon tetrachloride or chloroform at atemperature of 5 to 0 C. yielding disulfenyl chlorides Cl-S-Z-S-Cl (B).The Group B compounds, which were not isolated, react readily withdesired mercaptans or thiophenols after removal of sulfur chlorides(S,Cl and SC1 which are formed during the chlorination of the CBT.

These reactions are advantageously carried out in inert solvents such ascarbon tetrachloride or chloroform. The chlorination of CBT products onthe other hand in acetic acid and in the presence of a trace amount ofwater gives good yields of the corresponding bis-sulfonyl chlorides ofGroup C. This procedure of preparing sulfonyl chlorides is well known,however, the bis-sulfonyl chlorides thus obtained are new compositionsof matter and are useful compounds in a variety of reactionsparticularly in the preparation of bis-sulfonamides (see table 1V). itwill be appreciated by those skilled in the art that a very large numberof reactions can be performed with the novel sulfonyl chlorides.Briefly, such reactions could embrace hydrolysis, reactions withalcohols and phenols, with ammonia and amines, reactions with salts oforganic acids and particularly the ready reactions with aromatichydrocarbon and some of their derivatives in the presence of aluminumchloride to give sulfones.

The new compounds that may be obtained from the Group A, B and Ccompoundsmay berepresent dby the formula 7777 m A X wherein X is alkoxyor chlorine; R is lower alkyl and Y is SH, SCl; SO cl. alkyl-monothio,alkyl-dithio,,

trichloroalkyldithio, arylmonothio, aryldithio, aryltrithio,sulfonamido, alkyl sulfonamido, cycloalkyl-sulfonamido or aroyl-thio.Specific examples embraced by the general formula are Aromatic Dithiols1:4-Dimethoxyphenylene-2:S-dithiol 1 :4-Diethoxyphenylene-2 :S-dithioll:4-Dibutoxyphenylene-2:S-dithiol 4-Ethoxylrriethoxyphenylene-2:5-dithiol 4-Chlorol methoxyphenylene-2:6-dithiolAromatic Disulfonyl Chlorides 1:4-dimethoxyphenylene-2:S-disulfonylchloride l:4-Diethoxyphenylene-2:S-disulfonyl chloride Derivatives ofAromatic Dithiols Monothio derivativesl:4-Diethoxyphenylene-2:S-bis-(thiomethane) l:4-Diethoxyphenylene-2:5-bis-( thioethane)l:4-Diethoxyphenylene-2z5-bis-(thiol propane) l:4-Diethoxyphenylene-2:5-bis-(thio-2-propane)1:4Diethoxyphenylene-2:5bis-(thiol butane)1:4-Diethoxyphenylene-2:5-bis-( thio-2-butane)1:4-Diethoxyphenylene-2:5-bis-(thiol pentane)1:4-Diethoxyphenylene-2:5bis-(thiol hexane)1:4-Diethoxyphenylene-2:S-bis-(thiocyclohexane) 1:4-Diethoxyphenylene-2:S-bis-(thiobenzoyl) l :4-Diethoxyphenylene-2:5-bis-(thimp-nitrobenzene) Dithio derivativesl:4-Diethoxyphenylene-2:5bis-(dithiotrichloromethane)lz4-Diethoxyphenylene-2 :5-bis-( dithio-o-nitrobenzene)l:4-Diethoxyphenylene-2:5-bis-(dithio-2:4-nitrobenzene)1:4-Diethoxyphenylene-2 :5-bis-(dithio-2-nitro-4- chlorobenzene)1:4-Diethoxyphenylene-2:S-bis-(dithio-pentachlorobenzene) Trithioderivatives l:4-Diethoxyphenylene-2:5-bis-(trithio-9-anthracene)Derivatives of Aromatic Disulfonyl Chloride l:4-Dimethoxyphenylene-2:5bis-sulfonamidel:4-Diethoxyphenylene-2:5-bis-(n-butylsulfonamide) 1:4-Diethoxyphenylene-2:5bis-(dicyclonexylsulfonamide) The invention willnow be described by several examples, it being understood, however, thatthese examples are given by way of illustration and not by way oflimitation and that many changes may be effected without affecting inany way the scope and spirit of the invention as recited in the appendedclaims.

In each of examples l5, the catalyst used was the Girdler Catalyst KSF/Opreviously referred to.

EXAMPLE 1 Preparation of Cyclic Bi (2,5-bis-dithio-l ,4-dimethoxybenzene) R=CH X=-0CH in (l) 1,4-dimethoxybenzene (966 g, 7.0moles), methylene dichloride (1,500 cc.), sulfur monochloride (938 g.,7.0

9 moles) and catalyst (70 lfiflereiit'ixd' and heated on a steam bath. Agreen coloration developed and HCl evolved copiously; HCl liberationgradually subsided by the end of 6 hours. The reaction mixture was thenfiltered hot through a .Buchner funnel, thereby removing any unreactedstarting 1 materials which are soluble in the solvent. The orangecrystal- .line filtrate which was contaminated with catalyst weighted1,035 g. This material is extremely insoluble and was removed :from thecatalyst by soxhlet extraction with toluene to give 1 52.2 percent yieldof an orange solid which melts with vitrifaction 2l0-2l2. The materialmay be recrystallized from monochlorobenzene or from toluene as orangeplates M.pt. .2l2-214C.

EXAMPLE 2 Preparation of Cyclic Bi(2,5-bis-dithio-1,4-diethoxybenzeneR=C H X=OC H in (1) 1,4-diethoxybenzene (332 g., 2.0 moles) methylenedichloride (500 cc.), sulfur monochloride (268 g., 2.0 moles) andcatalyst (20 g.), were mechanically stirred for 16 hours. Severalminutes after mixing of the reactants, a slight exotherm reaction isnoted, accompanied by copious evolution of hydrogen chloride gas. At theend of 16 hours the reaction mixture was warmed to 40 C. for 1 hour,then cooled down to room temperature. Filtration yielded 234 g. oforange crystalline solid mixed with catalyst. Extraction with chloroformyielded 144 g. of product (59.5 percent yield), M.pt. 185-7 withvitrifaction after several recrystallizations from chloroform.

EXAMPLE 3 Preparation of Cyclic Bi(2,5-bis-dithio-4-ethoxy-anisoleR=CH,,, XOC l-l in (I) 4-ethoxyanisole (76 g.,0.5 mole) 036210326chloroform (125 ml.), ml.), sulfur monochloride (67 g., 0.5 mole), andcatalyst (5 g.) were mixed, and mechanically stirred at room temperaturefor 4 hours, during which time hydrogen chloride evolved copiously. Themixture was then heated on a steam bath for an hour and filtered hot toremove the catalyst. The condensed and cooled filtrate was thenchromatographed on an alumina column using chloroform as eluent. Thebright yellow main fraction was solvent stripped. The orange plasticresidue possessed a strong odor of 4-ethoxyanisole. A single wash withdiethyl ether caused precipitation of fine orange crystals which meltedat 158-60 C. with vitrifaction. Recrystallization from cyclohexaneseveral times gave large orange crystals in 60 percent yield, M.pt.156-8 with vitrifaction.

EXAMPLE 4 Preparation of Cyclic Bi(2,6-bis-dithio-4-chloroanisole) R=CHX=C l 4-chloroanisole (l42g., 1.0 mole), carbon tetrachloride (250 cc.),sulfur monochloride (134 g., 1.0 mole) and catalyst g.), were mixed andrefluxed on a steam bath until no more hydrogen chloride evolved. Thereaction mixture was then filtered hot to remove the catalyst. Theresulting filtrate was vacuum-stripped of solvent to leave a dark,gold-colored oil, which was chromatographed on alumina using benzene aseluent. The bright yellow main fraction was partially solventstrippedand left to stand overnight. The yellow precipitate which formed wascollected, recrystallized twice from benzene, and yielded bright yellowneedles, M.pt. 182 C.

EXAMPLE 5 Preparation of Cyclic Bi-(2,5-bis-dithio-l ,4-dibenzyloxybenzene) 1,4-dibenzyloxybenzene (58 g., 0.2 mole), methylenedichloride (200 ml.), sulfur monochloride (27 g., 0.2 mole) and catalyst(2 g.) were mixed and refluxed for 4 hours. The reaction mixture wasfiltered hot to remove the catalyst. The resulting filtrate wasvacuum-stripped of solvent. The yellow orange residue was twicechromatographed on alumina with chloroform as eluent in the firstinstance and benzene as eluent on the second column. The yellow residuewas recrystallized several times from benzene to yield 3 g. (4 percentyield) of tiny yellow crystals M.pt. l72-5 C. with vitrifaction.

EXPERIMENTAL SECTION IN RESPECT TO DEGRADATION OF CBT Tables II, III andIV list the new compositions of matter which have been prepared fromCBT. The new compounds have been fully characterized analytically. Beloware listed some general and specific examples.

GENERAL REACTIONS Reduction of CBT to aromatic dithiols of Group AExamples are listed below of some reduction runs of some CBT compoundsusing benzene as the solvent medium (table II).

R X in 1 Time (hrs) Temp. C. p.s.i.g.

ocit, OCH, con, 00,, oc,n. 0cm, OCJI, ocn, OCH, 0GB, 00,".

Chlorination of CBT in anhydrous media to disulfenyl chlorides of GroupB CBT (10 g.) in chloroform (50 cc.) was cooled to 50 C. in an ice/waterbath. Chlorine was bubbled until the orange solution assumed a rubyredcoloration. This procedure lasted about 30 minutes. The solvent andsulfur chlorides S Cl and SC1 which were formed were removed undervacuum distillation at around 30 C. when a red oil was obtained. Thiswas the disulfenyl chloride of Group B. These products could be usedwithout further purification as intermediates in preparing bisdisulfidesR"'-SSZ-SS-R' by reacting the disulfenyl chlorides with appropriatemercaptan or thiophenols in either chloroform or carbon tetrachloride.Table 111 lists such possible products where x=2. Chlorination of CBT inacetic acid with a trace -of water present to yield disulfonyl chloridesof Group C Through CBT (10 g.) in glacial acetic acid (250 cc.) andwater (20 cc.), chlorine gas was bubbled at a slow rate without allowingthe temperature to rise above 45 C. Chlorination was carried out forabout minutes. The orange crystalline CBT gradually disappeared and apale yellow white disulfenyl chloride appeared instead. The product wasfiltered and may readily be used as an intermediate in a variety ofpossible reactions as discussed herein. Table IV lists some of thederivatives prepared and analytically characterized.

EXAMPLE 6 Method of preparing bis-alkylthio derivatives Dialkyl sulfate(1 mole) or alkyl halide (2 moles) is added to the aromatic dithiol (1mole) in 20 percent sodium hydroxide solution (0.4 kg. solution permole). The reaction mixture was refluxed for 1 hour. The mixture wasthen cooled in an ice bath. Crude alkyl sulfide was then collected byfiltration and recrystallized from ethanol R-S-Z-S-R where Z is adisubstituted phenylene radical such as 1:4 diethoxyphenyleneradical andR is lower alkyl, straight chain, branched chain or cyclic structurecomprising from one to six carbon atoms.

S IC EACT QN Analytical data for all the compounds are listed in Tables[1, III and 1V.

EXAMPLE 7 mfiisnsztl= rs st ua lsv 9 23?: zis-uh w t Dimethyl sulfate(12.6 g., 0.1 mole) was added to 1:4 diethoxyphenylene 2:5-dithiol (11.5g., 0.05 mole) in 20 g. sodium hydroxide sodium solution (4 g. NaOl-l,0.1 mole) and the mixture was refluxed l hour. After cooling in an icebath for one-half hour, the crude solids were filtered and washedseveral times with water. Recrystallization from ethanol gave 9 g. (70percent yield) of yellow crystals, M.pt. l09-111 C.

Preparation of 1:4-diethoxyphenylene 2:5-bis-(thiobenzoyl)1:4-diethoxyphenylene 2:5-dithiol (5 g.) were dissolved in 20 cc. ofsodium hydroxide solution (25 percent), to which benzoyl chloride (25cc.) were added. The mixture was shaken vigorously under evolution ofheat. The oil which is formed soon crystallizes to a white solid. Thissolid was then filtered and washed several times with hot water andrecrystallized from benzene/cyclohexane until a constant melting pointwas obtained. M.pt. 180-l 8 1 C.

EXAMPLE 9 Preparation ofl:4-diethoxyphenylene-2:S-bis-(thio-pnitrobenzene) 1:4-diethoxyphenylene2:5-dithiol (2.3 g.) in ethanol (100 cc.) were added to 3.2 g. ofp-chloronitrobenzene in ethanol (50 cc.) and water (20 cc.). The mixturewas heated until all solids dissolved. Ten cubic centimeters of 6 N.solution of sodium hydroxide was then added. The resulting deep redsolution was refluxed. Precipitation appeared after about 10 minutes butthe mixture was refluxed for about a half hour. The reaction mixture wasthen allowed to cool and the yellow bis-monosulfide was filtered. CrudeM.pt. 199-200. Recrystallization from benzene and cyclohexane gaveyellow needles, M.pt. 205-206.

l O l EXAMPLE 10 Preparation of 1:4-diethoxyphenylene2:5-bis-(dithiotrichlorom ethane) EXAMPLE 1 1 Preparation of1:4-diethoxyphenylene 2:5-bis- (dithiopentachlorobenzene) To1:42:5-dithiol (5.6 g.) in carbon tetrachloride (50 cc.) was addedslowly with stirring pentachlorobenzenesulfenyl chloride (12.8 g.) incarbon tetrachloride cc.). Hydrogen chloride began evolving and themixture was refluxed until no more hydrogen chloride gas evolved. Onevaporating the solvent, substantially quantitative yield of the productis obtained. Crude M.pt. 201-4. Recrystallization from carbontetrachloride and petroleum either gave M.pt. 205.

002m 01 or 01 Q? l EXAMPLE12 Preparation of 1:4-diethoxyphenylene-2:S-bis-(trithioanthracene) To a solution oflz4-diethoxyphenylene 2:5-dithiol (6.9 g.) in chloroform (100 cc.) wereadded 9-chlorodithio anthracene (R-S-S-cl. R=9 anthryl) (16.6 g.) inchloroform (100 cc.) and the mixture was refluxed for 30 minutes.Hydrogen chloride gas evolved and refluxing was maintained untiltermination of gas evolvement. The chloroform was evaporated and theorange product chromatographed on alumina using benzene as eluent.- Theproduct on recrystallization from cyclohexane/benzene has a M.pt. of-166.

Preparation of l:4-diethoxyphenylene2:5-disulfonyl chloride CBT wassupplied in the form of bis-(p-diethoxyphenylene tetrasulfide) (4 g.) inacetic acid (100 cc.). Ten cubic centimeters of water were added andchlorine gas was bubbled through the mixture. The temperature was notallowed to rise above 45 C. Chlorination was continued for 75 minuteswhen straw-colored crystals appeared. Crude yield was 3.5 g. ofdisulfonyl chloride, M.pt. 189-190. Recrystallization from cyclohexanegave pale yellow crystals, M .pt 190 1 91 7 SOzCl ClSO2 Example 14Preparation of 1:4-diethoxyphenylene bis-(2:5-dicyclohexylsulfonamide)EXAMPLE 15 Preparation of the bis-sulfenyl chloride by chlorination ofthe CBT product or the dithiol.

The example discussed hereinabove refers to the chlorination of thedithiol. The use of the dithiol avoids any by products such as sulfurchlorides being formed. Thus l:4-diethoxyphenylene-2:S-dithiol (4.6 g.)in carbon tetrachloride cc.) was cooled in ice to 0". To this solutionwas added an ice cold solution of chlorine (2.8 g.) in carbontetrachloride (100 cc.), gradually with constant shaking. Hydrogenchloride gas evolved and the solution assumed a red color. The solventwas then removed under vacuum on a steam bath and a red fuming oil wasobtained which is the disulfenyl chloride. This may be used as anintermediate by reacting it with two moles of a mercaptan or thiol in aninert solvent. Thus adding pentachlorothiophenol in methylene dichloridewith stirring to the above prepared disulfenyl chloride followed bygentle warming and subsequently refluxing until all evolution ofhydrogen chloride gas ceased,

resulted in the preparation of l:4-diethoxyphenylene2z5-bis:

(dithio-pentachlorobenzene); M.pt. 204. This product was identical tothat obtained from the reaction of 1:4-diethoxyphenylene-225-dithiol andpentachlorobenzenesulfenyl chloride. See example 1 1.

EXAMPLE l6 Herbicidal Activity Weeds reduce crop yields and interferewith harvesting a quality crop. Herbicides have been shown to be usefultools to control undesirable foliage on agricultural land. The group Aand B compounds of the present invention may be successfully used asherbicides to control young weed seedlings. The chemicals arespecifically useful in controlling undesirable foliage. The followingmethods were employed to test the herbicidal activity.

A spray solution containing 2,000 parts per million of chemical to waterwas made by first dissolving two-tenths of a gram of chemical in 5 ml.of acetone and 30 mg. of isooctyl phenyl polyethoxy ethanol. Thispreparation was then TABLE V Dithiols Application Rate p.p.n1. k WeedControl Broad leaf G rass No. l 2000 90 N0. 2 2000 97 50 N0. 3 2000 I0075 Compound No. I had the following composition:

CzH5

Compound No. 3 had the following composition:

i O l Fungicidal Activity The control of foliage diseases on plants isessential in order to prevent crop failure from epidemic diseases, andto maintain good yield and quality of agricultural produce so thatrequirements for marketing and consumption can be met.

Group C compounds were evaluated as foliage fungicides by their abilityto protect plants from subsequent infection by fungus diseases.

One gram of the chemical to be tested was ground with 3 ml. of acetoneand 50 mg. of a nonionic surface-active agent (a Triton X-lOOcondensation product of an alkyl phenol and ethylene oxide). The acetoneand surface-active agent are known to be inactive in the biologicaltests run. The mixture was diluted with water, giving suspensionscontaining 500 and 1 2,000 p.p.m. of the chemical. These suspensionswere sprayed on duplicate 6-inch tomato plants (variety Clarks EarlySpecial) using a gun-type sprayer which delivered 2.5 ml. per second.The plants were then placed in the greenhouse, together with untreatedcheck plants. Twenty-four hours later the treated and untreated checkplants were inoculated with a suspension of Alternaria solani spores bymeans of a 20 second spray from an atomizer sprayer (delivery rate 1 ml.per second). The plants were then kept overnight in a controlled chamberat a temperature of 75 F. and 100 percent relative humidity. In themorning the plants were transferred to the greenhouse. Three days laterthe disease was scored by comparing the number of disease lesions of thetreated plants with the untreated check.

The formula to determine percent control is:

100 Avg. No. lesions on treated plant Avg. No. lesions on untreatedplant percent control The results are listed in the following table V1.

From the above table it may be seen that these compounds, as an example,have pronounced fungicidal activity in controlling Alternaria EarlyBlight disease of tomatoes by foliar application of the chemicals.

Disulfenyl chlorides of group B The compounds of group B (disulfenylchlorides) are normally used in situ and will yield, on reacting withthiols, compounds similar to types which also are obtained by reactingthe dithiols of group A mentioned previously with sulfenyl chlorides.For example:

Therefore the derivatives mentioned above are applicable. What isclaimed is: 1. A polysulfur compound of the formula wherein X is OR orchlorine and R is straight or branched alkyl of from one to five carbonatoms or benzyl, and wherein the indicated lower sulfur chain isattached at the 5-positions of the aromatic rings when X=OR and isattached at the 6- positions of the aromatic rings when X chlorine.

2. A polysulfur compound as claimed in claim 1, wherein the two sulfurchains are linked in para position to the aromatic rings.

3. A polysulfur compound as claimed in claim 1, wherein the two sulfurchains are linked to the aromatic rings in position 2:6.

4. Cyclic Bi(2,5-bis-dithio-l,4-dimethoxybenzene). 5. Cyclic Bi(l,5-bis-dithio-1,4-diethoxybenzene). 6. CyclicBi(2,5-bis-dithio-4-ethoxyanisole). 7. CyclicBi(2,6-bis-dithio-4-chloroanisole). 8. Cyclic Bi(2,5-bis-dithiol,4-dibenzyloxy-benzene 9. A process of preparing compounds of theformula wherein X is alkoxy, alkylthio or halogen and R is straight orbranched alkyl as set forth in claim 1, which comprises reacting aparasubstituted alkoxy benzene with sulfur monochloride in the presenceof an inert diluent and a Lewis acid type catalyst, and removing thereaction product from the reaction mixture.

10. A process as claimed in claim 9, wherein the reaction is carried outwithin a temperature range of from about 40-70 C.

11. A process as claimed in claim 9, wherein the reaction is carried outat the boiling temperature of the diluent.

12. A process as claimed in claim 9, wherein the diluent is ahalogenated aliphatic hydrocarbon solvent or carbon disulfide.

13. A process as claimed in claim 9, wherein said para-substitutedalkoxybenzene and said sulfur monochloride are cmploycd in substantiallystoichiometric amounts.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,621,032 Dated November l6 1971 Inventor(s) Zaven S. Ariyan and RobertL. Martin It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shovm below:

Claim 5 should read:

--5 Cyclic Bi (2Q5-bis-dithio-l,h-diethoxybenzene) Signs-"3 find sealedthis 30th day of May 1972.

(SEAL) Attest:

EDI'JAHD PLFLETCHER,JR. ROBERT GOTTSCHALK A; testing OfficerCommissioner of Patents

2. A polysulfur compound as claimed in claim 1, wherein the two sulfurchains are linked in para position to the aromatic rings.
 3. Apolysulfur compound as claimed in claim 1, wherein the two sulfur chainsare linked to the aromatic rings in position 2:6.
 4. CyclicBi(2,5-bis-dithio-1,4-dimethoxybenzene).
 5. CyclicBi(1,5-bis-dithio-1,4-diethoxybenzene).
 6. CyclicBi(2,5-bis-dithio-4-ethoxyanisole).
 7. CyclicBi(2,6-bis-dithio-4-chloroanisole).
 8. CyclicBi(2,5-bis-dithio-1,4-dibenzyloxy-benzene).
 9. A process of preparingcompounds of the formula
 10. A process as claimed in claim 9, whereinthe reaction is carried out within a temperature range of from about40*-70* C.
 11. A process as claimed in claim 9, wherein the reaction iscarried out at the boiling temperature of the diluent.
 12. A process asclaimed in claim 9, wherein the diluent is a halogenated aliphatichydrocarbon solvent or carbon disulfide.
 13. A process as claimed inclaim 9, wherein said para-substituted alkoxybenzene and said sulfurmonochloride are employed in substantially stoichiometric amounts.